WO2009079826A1 - Élastomère de polyuréthane thermoplastique présentant une stabilité hydrolytique et procédé de préparation - Google Patents

Élastomère de polyuréthane thermoplastique présentant une stabilité hydrolytique et procédé de préparation Download PDF

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Publication number
WO2009079826A1
WO2009079826A1 PCT/CN2007/003604 CN2007003604W WO2009079826A1 WO 2009079826 A1 WO2009079826 A1 WO 2009079826A1 CN 2007003604 W CN2007003604 W CN 2007003604W WO 2009079826 A1 WO2009079826 A1 WO 2009079826A1
Authority
WO
WIPO (PCT)
Prior art keywords
diisocyanate
thermoplastic polyurethane
organic
polyurethane elastomer
hydrolysis
Prior art date
Application number
PCT/CN2007/003604
Other languages
English (en)
Chinese (zh)
Inventor
Richard Wang
Jerry Fu
George Zhang
Maxy Yang
Louie Liu
David Zhao
Cosmo Wang
Becky Wang
Jack Ma
Original Assignee
Wanthane Polymers Co., Ltd.
Yantai Wanhua Polyurethanes Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanthane Polymers Co., Ltd., Yantai Wanhua Polyurethanes Co., Ltd. filed Critical Wanthane Polymers Co., Ltd.
Priority to PCT/CN2007/003604 priority Critical patent/WO2009079826A1/fr
Publication of WO2009079826A1 publication Critical patent/WO2009079826A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups

Definitions

  • the present invention relates to a thermoplastic polyurethane elastomer having hydrolytic stability containing a hydrolysis-resistant auxiliary agent and a process for producing the same. . Background technique
  • Thermoplastic polyurethane elastomer has the advantages of rubber and plastic, and has excellent comprehensive performance. It is widely used in the fields of shoe materials, pipes, fire hoses, oil pipelines, melt-spun spandex, sealing rings, etc., but its hydrolytic stability. Poor, the scope of application is limited.
  • thermoplastic polyurethane elastomers The reason for the poor hydrolysis stability of thermoplastic polyurethane elastomers is that after water penetrates into the elastomer
  • thermoplastic polyester elastomer Structure changing the thermoplastic polyester elastomer Structure, but due to its complicated process, high cost, and also weakened the inherent properties of thermoplastic polyester elastomer, it is limited in application; Second, it is a chemical additive, which is widely used in industry.
  • the hydrolysis-resistant additives mainly include epoxy compounds and carbodiimides.
  • the epoxy compounds can be roughly classified into two types: glycidyl derivatives and hydrocarbon-substituted oxirane compounds. The mechanism of action is as follows:
  • the epoxy compound acts as a proton acceptor and "seamage" in the elastomer, and can convert both the terminal carboxyl group and the terminal hydroxyl group (or amino group); however, it is used in a large amount and easily affects other properties of the material.
  • the carbodiimide compounds are as follows: di- 2-phenylcarbodiimide, di- 1-(4-chloronaphthyl)carbodiimide, oligocarbodiimide, etc., and the mechanism of action is as follows:
  • the carbodiimide captures the carboxylic acid groups produced during the hydrolysis, eliminates the catalytic hydrolysis of the carboxylic acid, and also has a "seam, or recoupling effect on the ruptured polyester PU chain, so the carbodiimide compound acts as a water resistant Decomposition aids are widely used.
  • Low-molecular weight compounds such as monocarbodiimide are easily decomposed during processing, produce irritating odor components, cause environmental pollution, or decrease due to gasification, so that the addition effect is not obvious. Therefore, polycarbodiimides are currently being used more and more.
  • ZL03106134. 6 discloses a mixture of carbodiimide and a process for preparing a polyurethane comprising an ester structure-containing compound and a carbodiimide having 12 to 4 Gwt% of ethylene oxide units. Although the hydrolysis resistance of the material is improved, the preparation process of the additive is complicated and expensive, and the production cost of the polyurethane elastomer is greatly increased.
  • U.S. Patent No. 3,714, 502 discloses a method of adding a small amount of acid silica to improve the hydrolytic stability of the polyurethane.
  • the method is applied to a thermoplastic polyurethane elastomer, particularly a porous polyurethane elastomer, the acid silica is difficult to disperse uniformly.
  • US Pat. No. 6,529,266 discloses a process for the preparation of a thermoplastic polyurethane elastomer which is first mixed with a polyol or a mixture of TPUs prepared from different polyols, which allows the producer
  • the complexity of the art has led to a significant increase in production costs.
  • the present invention provides a thermoplastic polyurethane elastomer having hydrolytic stability and a process for producing the same.
  • thermoplastic polyurethane elastomer of the present invention comprises a hydrolysis-resistant auxiliary agent and a thermoplastic polyurethane elastomer body, wherein the hydrolysis-resistant auxiliary agent is a carbodiimide-modified organic diisocyanate; preferably a carbodiimide-modified liquefied organic second Isocyanate; thermoplastic polyurethane elastomer body refers to various thermoplastic polyurethane elastomers conventional in the art without hydrolysis-resistant additives; carbodiimide modification means that organic diisocyanate partially removes carbon dioxide under the action of a catalyst. A carbodiimide group and a small amount of a uretonimine group.
  • the hydrolysis-resistant auxiliary of the present invention is further preferably a carbodiimide-modified liquefied diphenylmethane diisocyanate (also referred to as liquefied MDI) which converts the -NH 0 group moiety in diphenylmethane diisocyanate into
  • liquefied MDI liquefied liquefied diphenylmethane diisocyanate
  • thermoplastic polyurethane elastomer 05-50%; further preferably 1-15 of the weight of all organic diisocyanates in the thermoplastic polyurethane elastomer, in the present invention, the amount of the organic diisocyanate in the thermoplastic polyurethane elastomer is 0. %.
  • the calculation method of the amount of the hydrolysis-resistant auxiliary agent used in the present invention is:
  • the amount of the carbodiimide-modified organic diisocyanate used in the present invention accounts for the modification of the carbodiimide in the thermoplastic polyurethane elastomer containing the hydrolysis-resistant auxiliary agent. Weight percent of total organic diisocyanate and organic diisocyanate.
  • thermoplastic polyurethane elastomer of the present invention may be any type of thermoplastic polyurethane elastomer, but is preferably a polyester type or a polyether type.
  • thermoplastic polyurethane elastomer of the present invention is mainly prepared from a linear macromolecular diol, an organic diisocyanate, a chain extender and a hydrolysis resistant auxiliary agent under the action of a catalyst; it may further comprise other than the above enumerated Raw materials and chemical additives, such as stabilizers, Antioxidants, etc.
  • the linear macrodiol is selected from the group consisting of polyester diols or polyether diols or combinations thereof, wherein the polyester diol is a small molecule dicarboxylic acid and a small molecule binary The reaction product of an alcohol.
  • Suitable dicarboxylic acids may be aliphatic, alicyclic or aromatic dicarboxylic acids which generally contain a total of from 4 to 15 carbon atoms.
  • Suitable dicarboxylic acids may be succinic acid, pentane Diacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid or cyclohexanedicarboxylic acid, etc., may also be the above
  • An acid anhydride of a dicarboxylic acid such as phthalic anhydride, terephthalic anhydride or the like
  • a suitable glycol may be an aliphatic, aromatic diol which usually contains a total of 2 to 12 carbon atoms.
  • ethylene glycol 1, 2-propanediol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 10-decanediol, 1, 12-dodecanediol, etc.;
  • the polyester diol further includes a product obtained by reacting various lactones with a glycol, such as a polycaprolactone diol prepared by reacting caprolactone with diethylene glycol;
  • the polyester diol further includes a polycarbonate diol prepared by reacting a carbonate with a glycol;
  • the polyester diol of the present invention is preferably a polyester diol having a molecular weight of 500 to 10,000, further preferably having a molecular weight of 700 a polyester diol of -4000; when the polyester diol of the present invention is a polycarbonate diol, a polycarbonate diol having a molecular weight of 500 to 2,500 is preferred; and the polyester diol is further preferred in the present invention. It is a polyadipate type polyester diol.
  • the polyether diol is obtained by ring-opening polymerization of an epoxy compound in the presence of an active hydrogen compound as a starter and a catalyst.
  • the epoxy compound contains 2 to 6 carbon atoms, and may be, for example, polyethylene glycol formed by reacting ethylene oxide with ethylene glycol, polypropylene glycol formed by reacting propylene oxide with propylene glycol, by propylene oxide, and Poly(propylene glycol-ethylene glycol) formed by reacting ethylene oxide with propylene glycol or polytetramethylene glycol formed by reacting water with tetrahydrofuran; other suitable polyether polyols include polyether polyols of alkylene oxide Alcohols; Copolyethers can also be used in the present invention. Typical copolyethers include the reaction product of tetrahydrofuran with ethylene oxide or tetrahydrofuran with propylene oxide.
  • the polyether diol is preferably a polyether diol having a molecular weight from 500 to 10,000; more preferably 700-3000 molecular weight polyether diols; more preferably a polyether diol Polytetrahydrofuran ether glycol.
  • the organic diisocyanate may be an aromatic diisocyanate or an aliphatic/alicyclic diisocyanate or a combination thereof.
  • the aromatic diisocyanate is selected from the group consisting of diphenylnonane diisocyanate (MDI), m-phenylenediethylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene-1, 5-di
  • MDI diphenylnonane diisocyanate
  • XDI m-phenylenediethylene diisocyanate
  • TDI phenylene-1,4-diisocyanate
  • TDI toluene diisocyanate
  • aliphatic/alicyclic diisocyanate selected from isofluoride One or more of ketone diisocyanate (IPDI), 1, 4-cyclohexyl-diisocyanate (CHDI), decane-1, 10-di
  • the organic diisocyanate of the invention is preferably an aromatic diisocyanate, specifically selected from the group consisting of diphenylmethane diisocyanate (MDI), m-phenyldisionylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene - one or more of 1, 5-diisocyanate, diphenylmethane-3,3'-dimethoxy- 4,4,-diisocyanate and toluene diisocyanate (TDI); organic diisocyanate of the invention further Preferred is diphenylnonane diisocyanate, which is also known as pure MDI.
  • MDI diphenylmethane diisocyanate
  • XDI m-phenyldisionylene diisocyanate
  • TDI toluene diisocyanate
  • organic diisocyanate of the invention further Preferred is diphenylnonan
  • the catalyst of the invention is selected from the group consisting of organic or inorganic acid salts of cerium, tin, iron, lanthanum, cobalt, lanthanum, aluminum, zinc, nickel, lanthanum, molybdenum, vanadium, copper, manganese and zirconium or organometallic derivatives thereof and phosphines thereof And one or more of the organic tertiary amines; wherein the organic acid salt of tin or the organic metal 4 thereof is organotin, and the organic germanium is selected from the group consisting of stannous octoate, dibutyltin dioctoate and dibutyltin dilaurate One or more; the organic tertiary amine is selected from the group consisting of triethylamine, triethylenediamine, N, N, N, N, -tetramethylethylenediamine, N, N, hydrazine, N, -tetraethyl Ethylened
  • the chain extender of the present invention is a lower aliphatic or short chain diol having from about 2 to about 10 carbon atoms; specifically selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 4- Butylene glycol (BD0), 1,6-hexanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 4-cyclohexanedimethanol hydroquinone di-hydroxyethyl ether and new One or more of pentanediol; the chain extender of the present invention is further preferably 1,4-butanediol.
  • thermoplastic polyurethane elastomer containing the hydrolysis-resistant auxiliary agent of the present invention can be prepared by a method conventional in the art, such as mixing the hydrolysis-resistant auxiliary agent of the present invention with the raw material of the thermoplastic polyurethane elastomer body, using a prepolymer method, a conveyor belt method or a double Prepared by the screw reaction extrusion method, that is, the TPU product is obtained; however, the present invention is preferably prepared by the following method: adding the carbodiimide-modified organic diisocyanate to the organic diisocyanate, mixing uniformly, and then expanding with the macromolecular diol; The chain agent, the catalyst and the like are mixed and reacted in a certain ratio, and are prepared by a prepolymer method, a conveyor belt method or a twin-screw reaction extrusion method, that is, a TPU product is obtained.
  • thermoplastic polyurethane elastomer body Since the hydrolysis-resistant auxiliary agent of the present invention has good compatibility with the thermoplastic polyurethane elastomer body, the other aspects of the thermoplastic polyurethane elastomer body are not lowered by the addition of the hydrolysis-resistant auxiliary agent, so the thermoplastic polyurethane elastomer of the present invention is greatly While improving hydrolysis resistance, it still maintains other aspects of its original properties.
  • thermoplastic polyurethane elastomers of the present invention not only satisfy the requirements for hydrolysis resistance of low-end products on the market. Need: Such as general labor insurance shoes, air cushion, pneumatic tube and other fields; and because the hydrolysis-resistant additives in the invention are low in price (comparable to the price of pure MDI), there is no need to change the original production process, and no additional auxiliary equipment is needed. In this way, at least tens of thousands of yuan can be saved per ton of the product of the invention, the cost of the thermoplastic polyurethane elastomer of the invention is greatly reduced, and the product competitiveness is remarkably improved. detailed description
  • A a sample to which a hydrolysis resistant agent is added: prepared according to Example 1 of the present invention
  • Example 2 Sample without hydrolyzing agent: The same amount of liquefied MDI was replaced with pure MDI, except that it did not contain liquefied MDI, and the rest were identical to Example 1 of the present invention.
  • the TPU particles were injection molded into a sample having a thickness of about 2 ⁇ , and the hardness of the sample was measured to be 80 A Shore.
  • the sample is cut into a bell-type standard test strip, and then sample A and comparative sample B are simultaneously placed in a 70 ⁇ 2 ° C water tank for hydrolysis resistance test, every one week according to ASTM D412 (American Society for Testing and Materials The physical property test was carried out, and the results are shown in Table 1.
  • Example 2 Sample without hydrolysis resistance: The same amount of liquefied MDI was replaced with pure MDI, except that it did not contain liquefied MDI, and the others were identical to Example 2 of the present invention.
  • the TPU pellets were injection molded into a sample having a thickness of about 2 legs, and the hardness of the sample was measured to be 80 A Shore.
  • the sample was cut into a dumbbell-type standard test strip, and then sample C and comparative sample D were simultaneously placed in a water tank at 70 ⁇ 2 ° C for hydrolytic stability experiments, every other week according to ASTM D412 (American Society for Testing and Materials) Standard) Physical property test, the results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un élastomère de polyuréthane thermoplastique résistant à l'hydrolyse comprenant un diisocyanate organique modifié par carbodiimide utilisé comme matrice élastomère de polyuréthane thermoplastique. L'invention concerne également un procédé de préparation d'un élastomère de polyuréthane thermoplastique, consistant à mélanger des éléments résistant à l'hydrolyse et des matières premières pour la matrice élastomère de polyuréthane thermoplastique, puis à mettre en réaction le mélange au cours d'un procédé dans lequel est utilisé un prépolymère, un procédé sur bande transporteuse ou un procédé d'extrusion à double vis.
PCT/CN2007/003604 2007-12-14 2007-12-14 Élastomère de polyuréthane thermoplastique présentant une stabilité hydrolytique et procédé de préparation WO2009079826A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2007/003604 WO2009079826A1 (fr) 2007-12-14 2007-12-14 Élastomère de polyuréthane thermoplastique présentant une stabilité hydrolytique et procédé de préparation

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Application Number Priority Date Filing Date Title
PCT/CN2007/003604 WO2009079826A1 (fr) 2007-12-14 2007-12-14 Élastomère de polyuréthane thermoplastique présentant une stabilité hydrolytique et procédé de préparation

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109569628A (zh) * 2018-12-20 2019-04-05 常州大学 用于高效生产新戊二醇的催化剂的制备方法及新戊二醇的制备方法
CN113831583A (zh) * 2021-10-29 2021-12-24 盐城工学院 一种opusa复合气凝胶的制备方法及其应用
CN114634616A (zh) * 2022-03-31 2022-06-17 明达光电(厦门)有限公司 改性聚酯多元醇、其制备方法、及其制备的耐水解聚酯型tpu
CN115160534A (zh) * 2021-04-01 2022-10-11 财团法人工业技术研究院 水性聚氨酯

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3644456A (en) * 1964-08-12 1972-02-22 Upjohn Co Di((isocyanatobenzyl)-phenyl) carbodiimides and preparation of organic carbodiimides
US5246993A (en) * 1991-08-09 1993-09-21 Basf Aktiengesellschaft Oligomeric carbodiimides
CN1235964A (zh) * 1998-05-14 1999-11-24 巴斯福股份公司 基于1,3－双(1－甲基－1－异氰酸根合乙基)苯的碳化二亚胺
CN1721395A (zh) * 2004-07-13 2006-01-18 拜尔材料科学股份公司 低色数、含有碳二亚胺和/或脲酮亚胺基团、储存稳定的液体有机异氰酸酯的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3644456A (en) * 1964-08-12 1972-02-22 Upjohn Co Di((isocyanatobenzyl)-phenyl) carbodiimides and preparation of organic carbodiimides
US5246993A (en) * 1991-08-09 1993-09-21 Basf Aktiengesellschaft Oligomeric carbodiimides
CN1235964A (zh) * 1998-05-14 1999-11-24 巴斯福股份公司 基于1,3－双(1－甲基－1－异氰酸根合乙基)苯的碳化二亚胺
CN1721395A (zh) * 2004-07-13 2006-01-18 拜尔材料科学股份公司 低色数、含有碳二亚胺和/或脲酮亚胺基团、储存稳定的液体有机异氰酸酯的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI XUXIA ET AL.: "Synthesis of MDI-based Carbodiimide Hydrolyze-Resistant Reagent.", POLYURETHANE INDUSTRY., vol. 19, no. 1, 2004, pages 33 - 36 *
XU HAI-TAO ET AL.: "Preparation and hydrolysis stabilization of carbodiimide.", CHINA ELASTOMERICS., vol. 13, no. 6, 25 December 2003 (2003-12-25), pages 71 - 73 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109569628A (zh) * 2018-12-20 2019-04-05 常州大学 用于高效生产新戊二醇的催化剂的制备方法及新戊二醇的制备方法
CN115160534A (zh) * 2021-04-01 2022-10-11 财团法人工业技术研究院 水性聚氨酯
CN113831583A (zh) * 2021-10-29 2021-12-24 盐城工学院 一种opusa复合气凝胶的制备方法及其应用
CN114634616A (zh) * 2022-03-31 2022-06-17 明达光电(厦门)有限公司 改性聚酯多元醇、其制备方法、及其制备的耐水解聚酯型tpu
CN114634616B (zh) * 2022-03-31 2023-12-22 明达光电(厦门)有限公司 改性聚酯多元醇、其制备方法、及其制备的耐水解聚酯型tpu

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